Process to manufacture crosslinked polymers

ABSTRACT

The process according to the invention is performed by reaction of epoxide resins with primary and/or secondary polyamines with simultaneous quaternizing by means of aromatic and aliphatic polysulfonic esters, halogen-free organic phosphoric esters, or organic compounds which contain at least 1 chlorine or bromine atom, and which are free from -COOH groups and corresponding salt groups. The crosslinked plastics thus obtained are distinguished by an improved electrical conductivity.

The invention relates to crosslinked plastics which have for plastics anexceptionally high electrical conductivity.

Electrically conducting plastics have already been described in the U.S.Pat. Nos. 4,000,116 and 4,014,955. They are polyethers which containionic bonds and which are produced by reaction of Mannich bases, whichare derived from phenols, with epoxide compounds containing Cl or Bratoms, or with epoxide compounds and organic compounds containing Cl orBr atoms. Plastics of this type have however the disadvantage that theyall too readily swell in water. The products having the highestelectrical conductivity dissolve completely in water. Furthermore, thepossibilities of processing the starting mixtures are very limited byvirtue of the short gelling time.

To be mentioned as further prior art are U.S. Pat. Nos. 4,115,296 and3,312,636. Amine-cured epoxide resins are described in the former ofthese two patent specifications. The starting mixtures contain, besidesthe epoxide compound and the polyamine, fluorine- or chlorine-containingmonocarboxylic acid as accelerators. There is no mention of an increasein conductivity of the finished products or of quaternisation, which isunderstandable since the formation of quaternised products in the caseof fluorine-containing monocarboxylic acids was from the outset not tobe expected on account of the strong bond of the fluorine atoms.

The U.S. Pat. No. 3,312,636 concerns flameproof epoxide resins producedby reaction of butadiene polymers, which contain epoxide groups, witharomatic diamines and specific phosphoric esters of high halogencontent, these esters acting as fire-retarding agents. There is nomention of any increase in the electrical conductivity and it is evidentthat an increase is not intended to be brought about.

The production process according to the invention now enables plasticshaving a surprisingly good electrical conductivity to be obtained. Theseplastics have low water absorption, high conductivity and are largelyinsensitive to water. The starting mixture surprisingly has a gellingtime longer than that of the corresponding mixtures according to U.S.Pat. Nos. 4,000,116 and 4,014,955, and can therefore be more easilyprocessed.

The invention thus relates to a process for producing crosslinkedplastics by reacting

(a) an epoxide resin,

(b) a primary and/or secondary, aromatic, aliphatic or heterocyclicpolyamine, and

(c) a quaternising agent selected from the group comprising: aromaticand aliphatic polysulfonic acid esters, halogen-free organic phosphoricesters, and organic compounds which contain at least one chlorine orbromine atom in the molecule and which are free from groups of theformula --COOZ in which Z is hydrogen or a metal atom,

(d) optionally in the presence of customary additives for plastics,particularly fillers, and

(e) optionally in the presence of organic solvents,

there being in the starting reaction mixture, to 1 equivalent ofglycidyl groups, 0.5 to 1.5 equivalents of hydrogen atoms of thepolyamine stated under (b) which are bound to nitrogen, and, to 1 gramatom of N in the reaction mixture, a maximum of 1 gram equivalent of aquaternising agent.

A preferred process according to the invention for producing crosslinkedplastics comprises reacting

(a) an epoxide resin containing at least one N atom in the molecule,

(b) a primary and/or secondary, aromatic, aliphatic or heterocyclicpolyamine, and

(c) a quaternising agent selected from the group consisting of aromaticand aliphatic polysulfonic esters, halogen-free organic phosphoricesters, and organic compounds which contain at least 2 chlorine orbromine atoms in the molecule, and which are free from groups of theformula --COOZ in which Z is hydrogen or a metal atom,

(d) optionally in the presence of customary additives for plastics,particularly fillers, and

(e) optionally in the presence of organic solvents,

at a temperature of 50° to 150° C., there being in the starting reactionmixture, to 1 equivalent of glycidyl groups, 0.5 to 1.5 equivalents ofhydrogen atoms of the polyamine stated under (b) which are bound tonitrogen, and, to 1 gram atom of N in the reaction mixture, a maximum of1 gram equivalent of a quaternising agent.

According to a further preferred embodiment of the process according tothe invention, there is in the starting reaction mixture, to 1equivalent of glycidyl groups, 1 equivalent of hydrogen atoms of thepolyamine stated under (b) which are bound to nitrogen, and, to 1 gramatom of N in the reaction mixture, 1 gram equivalent of a quaternisingagent.

The process is preferably performed in the absence of organic solvents.

The starting products mentioned under (a), (b) and (c) for the processaccording to the invention can be used in each case as a mixture of therespective starting products.

The epoxide resin mentioned under (a) is preferably a compound of theformulae I-II ##STR1## wherein R is an aliphatic radical having 2 to 15C atoms, or an unsubstituted or substituted aromatic radical having alltogether 6 to 15 C atoms, R¹ is a glycidyl group, an aliphatic radicalhaving 1 to 10 C atoms, or an unsubstituted or substituted aromaticradical having all together 6 to 10 C atoms, and q is the number 0 or 1.

When R and R¹ are an aromatic radical, they can be unsubstituted orsubstituted by 1 or 2 C₁ -C₄ -alkyl groups, especially by methyl.

Particularly preferably used as the epoxide resin mentioned under (a) isa compound of the formula Ia or of the formula I or II wherein R is aphenylene group which is unsubstituted or substituted by 1 or 2 methylgroups, or the group ##STR2## q is the number 0 or 1, and R¹ is aglycidyl group.

Examples of preferred epoxide resins of this type are:N,N,N',N'-tetraglycidyl-methylenedianiline,N,N,N',N'-tetraglycidyl-m-phenylenediamine and -p-phenylenediamine,N-diglycidylaniline, -toluidine and -xylidine, and epoxide resins basedon 5,5-dimethylhydantion and based on m-, o- and p-aminophenol.

One of the polyamines mentioned under (b) preferably used is a compoundof the formula III

    R.sup.2 -(NH.sub.2).sub.n                                  (III),

a compound of the formula IV ##STR3## or a compound of the formula V##STR4## wherein n is one of the numbers 2, 3 or 4, R² is an n-valentaliphatic radical having 2 to 15 C atoms, an n-valent, unsubstituted orsubstituted, aromatic radical having all together 6 to 15 C atoms, or anunsubstituted or substituted heterocyclic radical having all together 3to 15 C atoms, R³ has the same definition as R¹ in the formula I but isnot a glycidyl group, and X and T are such organic radicals which canform with the two N atoms a 5- or 6-membered heterocyclic ring.

When R² and R³ are an aromatic radical or R² a heterocyclic radical,they can be unsubstituted or substituted by 1 or 2 C₁ -C₄ -alkyl groups,especially by methyl.

One of the polyamines mentioned under (b) particularly preferably usedis a compound of one of the formulae III to V, wherein n is the number2, R² is ethylene, hexamethylene, phenylene or the group ##STR5## whichcan be substituted on each of the benzene rings by C₁ -C₄ -alkyl, R³ isC₁ -C₄ -alkyl or phenyl, and X and T are ethylene.

Examples of these preferred polyamines are 4,4'-diaminodiphenylmethane,m-phenylenediamine, piperazine, 4,4'-diamino-3-ethyldiphenylmethane,4,4'-diamino-3,3'-diethyldiphenylmethane, compounds of the formulae CH₃--NH--(CH₂)₆ --NH--CH₃, ##STR6##

There is preferably used as one of the quaternising agents mentionedunder (c) a compound of the formula VI ##STR7## a compound of theformula VII or a compound of the formula VIII

    R.sup.2 --(COO--R.sup.6 --Cl).sub.n                        (VIII)

wherein n is one of the numbers 2, 3 or 4, R⁵ is hydrogen or has thesame meaning as R³ in the formula IV, R² has the same meaning as in theformula III, R⁴ is an n-valent aliphatic radical having 2 to 12 C atoms,and R⁶ is an aliphatic radical having 2 to 8 C atoms, or anunsubstituted or substituted cycloaliphatic radical having all together5 to 8 C atoms.

When R² is an aromatic or heterocyclic radical and R⁶ a cycloaliphaticradical, these can be unsubstituted or substituted by 1 to 2 C₁ -C₄-alkyl groups, especially by methyl.

A quaternising agent mentioned under (c) preferably used is a compoundof the formulae VI to VIII, wherein n is 2, R² is ethylene ortetramethylene, R³ is C₁ -C₄ -alkyl, R⁴ is a bivalent aliphatic radicalhaving 5 or 6 C atoms, R⁵ is hydrogen and R⁶ ethylene.

Examples of the quaternising agents are trimethylphosphate, toluene- orbenzenesulfonic esters of glycols, for example compounds of the formulae##STR8## Cl--CH₂ OOC--(CH₂)₄ --COOCH₂ CH₂ --Cl, ##STR9## Cl--CH₂ CH₂OOC--CH₂ CH₂ --COOCH₂ CH₂ --Cl and OP(OCH₂ CH₂ CH₃)₃.

In the preferred form of the process according to the invention, thereare used as the epoxide resin mentioned under (a) the compound of theformula ##STR10## (N,N,N',N'-tetraglycidyl-methylenediamine) as one ofthe polyamines mentioned under (b) one of the compounds of the formulae##STR11## as one of the quaternising agents mentioned under (c) one ofthe compounds of the formulae ##STR12## Cl--CH₂ CH₂ --OOC--(CH₂)₄--COO--CH₂ CH₂ --Cl

and (d) aluminium oxide as filler.

In a particularly preferred form of the process according to theinvention, there are used as the epoxide resin mentioned under (a) thecompound of the formula ##STR13## as one of the polyamines mentionedunder (b) 4,4'-diaminodiphenylmethane, or a mixture of4,4'-diaminodiphenylmethane, 4,4'-diamino-3-ethyl-diphenylmethane and4,4'-diamino-3,3'-diethyl-diphenylmethane, as one of the quaternisingagents mentioned under (c) bis-(β-chloroethyl)-adipic ester, and (d)aluminium oxide as filler.

All starting products usable in the process according to the inventionare known, and it is therefore unnecessary here to describe them or inparticular the manner of producing them.

To be mentioned as customary additives for plastics, which additives canbe used in the process according to the invention, are in particularfillers (for example silica gel, quartz powder, powdered slate,MgCa-silicate powder, baryta powder and aluminium oxide powder), dyesand flexibilisers.

Further subject matter of the present invention is the use of theplastics produced by the process according to the invention asantistatic materials, particularly in electrical apparatus and plants.In the case of objects and structures of large surface area, there islargely avoided in a simple manner by this application for example anelectrostatic charge. There is a need especially in modern directcurrent high-tension engineering for antistatic insulators which have notendency to become contaminated by electrostatic deposition of dustparticles.

The invention is further illustrated in the Examples which follow.

EXAMPLE 1

125 g of N,N,N',N'-tetraglycidyl-methylenedianiline having an epoxideequivalent weight of 133, 49.6 g of 4,4'-diaminodiphenylmethane and135.6 g of bis-(β-chloroethyl)-adipic ester are well mixed together; themixture is then melted at 80° C., degassed, poured into a mould ofdimensions 150×150×4 mm and, by stepwise heating at 80° C., 100° C. and120° C. (4 hours at each step), transformed into a hard moulded product,the properties of which are given in Table 1.

A small specimen of this product is pulverised and extracted withboiling water; there is found in the aqueous extract, by means oftitration with silver nitrate solution, 8.2% of chloride ions; thechlorine content of the cured product not extracted is 11.0%(determination according to Wurzschmitt).

EXAMPLE 2

29.5 g of the epoxide resin used in Example 1, 13.3 g of4,4'-diaminophenylmethane, 36.3 g of bis-(β-chloroethyl)-adipic esterand 120 g of aluminium oxide (particle size 1-30μ) are well mixed; themixture is melted at 80° C., degassed, and converted as in Example 1into a cured moulded product, the properties of which are summarised inTable 1.

EXAMPLE 3

30 g of the epoxide resin used in Example 1, 14 g of4,4'-diaminodiphenylmethane and 56 g of hexamethylenebisbenzenesulfonicester are well mixed; the mixture is melted at 80° C., degassed, andpoured into a mould as in Example 1. By stepwise heating at 120° C.,140° C., 160° C. and 180° C. (2 hours at each step), there is formedfrom the melt a hard moulded product, the properties of which aresummarised in Table 1. A small specimen of the product is pulverised,and extracted with boiling water; there is found in the aqueous extract,by titration with sodium hydroxide solution, 33.2% of benzenesulfonicacid (theoretical content: 42.3%).

Comparative Example

77.8 g of bisphenol-A diglycidyl ether (epoxide equivalent weight 194),62 g of dichlorohexane and 91.2 g of2,2',6,6'-tetrakis(dimethylaminomethyl-bisphenol-A are quickly mixed at60° C.; the mixture is subsequently degassed, poured into a mould ofdimensions 150×150×4 mm, and transformed, by stepwise heating at 60° C.,100° C. (2 hours) and 140° C. (12 hours), into a hard moulded product,the properties of which are given in Table 1; the specific current-flowresistance is 3.9.10¹⁰ [Ω.cm].

This comparative example shows that substances according to the U.S.Pat. No. 4,014,955 have indeed an increased conductivity compared withthat of normal epoxide resins, that however the processing possibility(gelling time) and water absorption are considerably less favourablethan in the case of the substances produced according to the invention.

                  TABLE 1                                                         ______________________________________                                                                     Water                                                              Dimensional                                                                              absorption                                                                             Gelling                                         Flexural  stability  after 4 days                                                                           time at                                 Example strength  under heat.sup.2                                                                         in water at                                                                            100° C.                          No.     (N/mm.sup.2).sup.1                                                                      (°C.)                                                                             23° C. (%)                                                                      (min.)                                  ______________________________________                                        1       36.6      71         0.12     34                                      2       30.4      69                                                          3       30.8      86         2.89     14                                      Compara-                                                                      tive    36        139        specimen 4.5                                     Example                      dissolved                                        ______________________________________                                         .sup.1 VSM 77 103 (VSM = Verband Schweizerischer Maschinenindustrieller)      (Association of Swiss Machine Manufacturers)                                  .sup.2 ISO/R (ISO = International Standards Organisation)                

EXAMPLES 4-21

The substances contained in Table 2 are mixed in a mortar ashomogeneously as possible; in each case 7 g (with filled mixtures 10 g)are cured in small aluminium dishes (diameter 5.5 cm) in the givenmanner. Table 2 shows the mixture proportions, the curing conditions andthe specific current-flow resistance.

The embodiment of Example 10 is most particularly preferred.

The starting substances in Table 2 have the following designations:

    __________________________________________________________________________    Epoxide resin I                                                                          = the epoxide resin used in Example 1,                             Epoxide resin II                                                                         = N,N,N',N'tetraglycidyl-p-phenylene-                                           diamine,                                                         Epoxide resin III                                                                        = epoxide resin based on 5,5-dimethyl-                                          hydantoin, having an epoxide equivalent                                       weight of 141,                                                   Epoxide resin IV                                                                         = epoxide resin based on p-aminophenol,                                         having an epoxide equivalent weight                                           of 98,                                                           Amine A    = the amine (4,4'-diaminodiphenylmethane)                                       used in Example 1,                                               Amine B    = m-phenylenediamine,                                              Amine C    =                                                                                ##STR14##                                                        Amine D   = piperazine,                                                      Amine E    =                                                                                ##STR15##                                                       Amine F    = a mixture of 4,4'-diaminodiphenyl-                                            methane, 4,4'-diamino-3-ethyl-diphenyl-                                       methane and 4,4'-diamino-3,3'-diethyl-                                        diphenylmethane,                                                 Quaternising agent a                                                                     = the quaternising agent used in                                                Example 3,                                                       Quaternising agent b                                                                     =                                                                                ##STR16##                                                       Quaternising agent c                                                                     = trimethylphosphate,                                              Quaternising agent d                                                                     = ClCH.sub.2 CH.sub.2 OOC(CH.sub.2).sub.4COOCH.sub.2 CH.sub.2                   Cl,                                                              Quaternising agent e                                                                     = ClCH.sub.2 CH.sub.2 OOCCH.sub.2 CH.sub.2COOCH.sub.2 CH.sub.2                  Cl.                                                              __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________    Mixture of                                                                       epoxide  quaternising                                                                         Filler wt. %    Specific current-flow                      Ex.                                                                              resin                                                                              amine                                                                             agent  relative to the resistance at 23° C.                No.                                                                              (mol)                                                                              (mol)                                                                             (mol)  total mixture                                                                         Curing  (Ω · cm)                    __________________________________________________________________________                               120/140/                                           4  I    A   a      --      160/180° C.                                                                    8.5 · 10.sup.11                      (0.035)                                                                            (0.055)                                                                           (0.07)         2h at each                                                                    step                                                                          120/140/                                           5  I    A   a      60 quartz                                                                             160/180° C.                                                                    1.8 · 10.sup.11                      (0.035)                                                                            (0.055)                                                                           (0.07) powder  2h at each                                                                    step                                                                          80/100/                                            6  I    A   b      60 Al oxide                                                                           120° C.                                                                        1.5 · 10.sup.11                      (0.035)                                                                            (0.055)                                                                           (0.07) neutral 4h at each                                                                    step                                                                          80/120/                                            7  I    A   c      --      140/160/                                                                              1.2 · 10.sup.10                      (0.066)                                                                            (0.066)                                                                           (0.06)         180° C.                                                                2h at each                                                                    step                                               8  I    A   d      --      80-120°  C.                                                                    5 · 10.sup.10                        (0.01)                                                                             (0.01)                                                                            (.02)                  8.3 · 10.sup.9 *                                             80/100/                                            9  I    A   d      60 Al oxide                                                                           120° C.                                                                        3.3 · 10.sup.9                       (0.01)                                                                             (0.01)                                                                            (0.02) neutral 4h at each                                                                    step                                                                          120/130/                                           10 I    A   d      60 Al oxide III                                                                       140/150° C.                                                                    2.1 · 10.sup.8                       (0.01)                                                                             (0.01)                                                                            (0.02)         2h at each                                                                    step                                                                          100 and                                            11 I    B   d      --      120° C.                                                                        6.0 · 10.sup.9                       (0.01)                                                                             (0.01)                                                                            (0.02)         6h at each                                                                    step                                                                          100 and                                            12 I    B   d      60 Al oxide                                                                           120° C.                                                                        6.6 · 10.sup.8                       (0.01)                                                                             (0.01)                                                                            (0.02) neutral 6h at each                                                                    step                                                                          100 and                                            13 II   B   d      --      120° C.                                                                        2.3 · 10.sup.10                      (0.01)                                                                             (0.01)                                                                            (0.02)         4h at each                                                                    step                                                                          100 and                                            14 II   B   d      60 silica gel                                                                         120° C.                                                                        5.8 · 10.sup.8                       (0.01)                                                                             (0.01)                                                                            (0.02)         4h at each                                                                    step                                                                          60/80/100/                                         15 I    C   e      --      120° C.                                                                        8.6 · 10.sup.11                      (0.01)                                                                             (0.015)                                                                           (0.03)         4h at each                                                 D                  step                                                       (0.005)                                                                                          1h at 80° C. +                              16 I    E   e      --      2h at 120° C. +                                                                8.1 · 10.sup.11                      (0.01)                                                                             (0.02)                                                                            (0.03)         4h at 140° C. +                                                        2h at 160° C.                                                          6h at 60° C.                                17 I    C   d      --      then    3.4 · 10.sup.8                       (0.01)                                                                             (0.005)                                                                           (0.03)         80/100/120                                                 D                  140° C. with                                        (0.015)            2h at each                                                                    step                                                                          80/100/                                            18 III  B   d      --      120° C.                                                                        1.3 · 10.sup.9                       (0.04)                                                                             (0.04)                                                                            (0.08)         4h at each                                                                    step                                                                          80/100/                                            19 IV   A   d      --      120° C.                                                                        4.3 · 10.sup.10                      (0.053)                                                                            (0.04)                                                                            (0.06)         4h at each                                                                    step                                                                          80/100/                                            20 IV   A   d      60 Al oxide                                                                           120° C.                                                                        6.3 · 10.sup.9                       (0.053)                                                                            (0.04)                                                                            (0.06) neutral 4h at each                                                                    step                                                                          80/100/                                            21 I    F   d      --      120° C.                                                                        8.8 · 10.sup.10                      (0.01)                                                                             (0.01)                                                                            (0.02)         4h at each                                                                            3.2 · 10.sup.9 **                                            step                                               __________________________________________________________________________     *after 1 day in water at 23° C.                                        **after 4 days in water at 23° C.                                 

What is claimed is:
 1. A process for producing crosslinked plasticswhich comprises reacting(a) an epoxide resin containing at least oneN-glycidyl group in the molecule, (b) a primary and/or secondary,aromatic, aliphatic or heterocyclic polyamine, and (c) a quaternisingagent selected from the group consisting of aromatic and aliphaticpolysulfonic esters, halogen-free organic phosphoric esters, and organiccompounds which contain at least 2 chlorine or bromine atoms in themolecule, and which are free from groups of the formula --COOZ in whichZ is hydrogen or a metal atom, (d) optionally in the presence ofcustomary additives for plastics, particularly fillers, and (e)optionally in the presence of organic solvents,at a temperature of 50°to 150° C., there being in the starting reaction mixture, to 1equivalent of glycidyl groups, 0.5 to 1.5 equivalents of hydrogen atomsof the polyamine stated under (b) which are bound to nitrogen, and, to 1gram atom of N in the reaction mixture, a maximum of 1 gram equivalentof a quaternising agent.
 2. A process according to claim 1, wherein inthe starting reaction mixture there is, to 1 equivalent of glycidylgroups, 1 equivalent of hydrogen atoms of the polyamine stated under (b)which are bound to nitrogen, and, to 1 gram atom of N in the reactionmixture, 1 gram equivalent of a quaternising agent.
 3. A processaccording to claim 1, wherein there is used, as the epoxide resin statedunder (a), a compound of one of the formulae I-II ##STR17## in which Ris an aliphatic radical having 2 to 15 C atoms, or an unsubstituted orsubstituted aromatic radical having all together 6 to 15 C atoms, R¹ isa glycidyl group, an aliphatic radical having 1 to 10 C atoms, or anunsubstituted or substituted aromatic radical having all together 6 to10 C atoms, and q is the number 0 or
 1. 4. A process according to claim1, wherein there is used, as one of the polyamines stated under (b), acompound of the formula III

    R.sup.2 --(NH.sub.2).sub.n                                 (III),

a compound of the formula IV ##STR18## or a compound of the formula V##STR19## in which n is one of the numbers 2, 3 or 4, R² is an n-valentaliphatic radical having 2 to 15 C atoms, an n-valent, unsubstituted orsubstituted, aromatic radical having all together 6 to 15 C atoms, or anunsubstituted or substituted heterocyclic radical having all together 3to 15 C atoms, R³ is an aliphatic radical having 1 to 10 C atoms, or anunsubstituted or substituted aromatic radical having all together 6 to10 C atoms, and X and T are such organic radicals that can form with thetwo N atoms a 5- or 6-membered heterocyclic ring.
 5. A process accordingto claim 1, wherein there is used, as one of the quaternising agentsstated under (c), a compound of the formula VI ##STR20## a compound ofthe formula VII ##STR21## or a compound of the formula VIII

    R.sup.2 --(COO--R.sup.6 --Cl).sub.n                        (VIII)

in which n is one of the numbers 2, 3 or 4, R⁵ is hydrogen, an aliphaticradical having 1 to 10 C atoms, or an unsubstituted or substitutedaromatic radical having all together 6 to 10 C atoms, R² is an n-valentaliphatic radical having 2 to 15 C atoms, or an n-valent, unsubstitutedor substituted, aromatic radical having all together 6 to 15 C atoms, oran unsubstituted or substituted heterocyclic radical having all together3 to 15 C atoms, R³ is an aliphatic radical having 1 to 10 C atoms, oran unsubstituted or substituted aromatic radical having all together 6to 10 C atoms, R⁴ is an n-valent aliphatic radical having 2 to 12 Catoms, and R⁶ is an aliphatic radical having 2 to 8 C atoms, or anunsubstituted or substituted cycloaliphatic radical having all together5 to 8 C atoms.
 6. A process according to claim 1, wherein there isused, as the epoxide resin stated under (a), the compound of the formula##STR22## as one of the polyamines stated under (b), one of thecompounds of the formulae ##STR23## as one of the quaternising agentsstated under (c), one of the compounds of the formulae ##STR24## Cl--CH₂CH₂ --OOC--(CH₂)₄ --COO--CH₂ CH₂ --Cland (d) aluminium oxide as filler.7. A process according to claim 1, wherein there is used, as the epoxideresin stated under (a), the compound of the formula ##STR25## as one ofthe polyamines stated under (b), 4,4'-diaminodiphenylmethane, or amixture of 4,4'-diaminodiphenylmethane,4,4'-diamino-3-ethyl-diphenylmethane and4,4'-diamino-3,3'-diethyl-diphenylmethane, as one of the quaternisingagents stated under (c) bis-(β-chloroethyl)-adipic ester, and (d)aluminium oxide as filler.
 8. A process according to claim 7, whereinthere is used, as the epoxide resin stated under (a), the compound ofthe formula ##STR26## as one of the polyamines stated under (b),4,4'-diaminodiphenylmethane, as one of the quaternising agents statedunder (c), bis-(β-chloroethyl)-adipic ester, and (d) aluminium oxide asfiller.
 9. A process according to claim 1, wherein the reaction isperformed in the absence of organic solvents.